CN103299403A

CN103299403A - Chemical solution for forming protective film

Info

Publication number: CN103299403A
Application number: CN2011800648019A
Authority: CN
Inventors: 斋尾崇; 公文创一; 斋藤真规; 荒田忍; 七井秀寿; 赤松佳则
Original assignee: Central Glass Co Ltd
Current assignee: Central Glass Co Ltd
Priority date: 2011-01-12
Filing date: 2011-12-28
Publication date: 2013-09-11
Anticipated expiration: 2031-12-28
Also published as: JP2013102109A; US8932390B2; US20140373870A1; US20120174945A1; KR20130116326A; WO2012096133A1; TW201231633A; KR101535200B1; SG190097A1; US9496131B2; TWI548730B; CN103299403B

Abstract

The invention provides a chemical solution for forming a protective film that forms a water-repellent protective film (10) so as to improve washing processes that are prone to inducing pattern collapse in a wafer (metal-based wafer) having a concavoconvex pattern formed on a surface thereof and having at least one of the elements titanium, tungsten, aluminum, copper, tin, tantalum, and ruthenium on the concave part (4) surfaces of the concavoconvex pattern. [Solution] This chemical solution for forming a protective film is a chemical solution containing a water-repellent protective film forming agent for forming a water-repellent protective film (10) on at least the concave part (4) surfaces before a drying process after a washing process for the metal-based wafer, and a solvent, and the chemical solution is characterized by the water-repellent protective film forming agent being a compound shown by general formula [1]. (R1 is a C1-18 monovalent hydrocarbon in which elemental fluorine may be substituted for part or all of the elemental hydrogen; R2 represents mutually independent monovalent organic groups containing C1-18 hydrocarbons in which elemental fluorine may be substituted for part or all of the elemental hydrogen; and a is an integer between 0 and 2.).

Description

Diaphragm forms uses chemical solution

Technical field

The present invention relates to the cleaning technique of the substrate (wafer) in semiconductor device manufacturing etc.

Background technology

In the semiconductor device that network, digital household appliances are used, require further high-performance/multifunction, low consumption electrification.Therefore the miniaturization of circuit pattern advances, and is accompanied by the propelling of miniaturization, and the pattern of circuit pattern topples over becomes problem.In semiconductor device is made, use to remove particle mostly, metal impurities are the matting of purpose, its result, matting account for 3～4 one-tenth of semiconductor manufacturing process integral body.In this matting, the depth-width ratio of pattern is followed the miniaturization of semiconductor device and when uprising, and after cleaning or washing, the phenomenon that pattern toppled over when gas-liquid interface was by pattern when wafer dry is pattern and topples over.

In the patent documentation 1, as suppressing the gimmick that pattern topples over, the technology that cleaning fluid is replaced into the 2-propyl alcohol before gas-liquid interface is by pattern by water is disclosed.But the depth-width ratio that it is said to have the pattern that can tackle is 5 with inferior boundary.

In addition, in the patent documentation 2, as suppressing the gimmick that pattern topples over, disclose the technology of corrosion-resisting pattern as object.Thereby this gimmick is to suppress the gimmick that pattern topples over by capillary force being reduced to the limit.

But, the technology of the disclosure be with corrosion-resisting pattern as object, resist self is carried out modification, and then finally can come along with resist and remove, therefore do not need to suppose the removal method of dried inorganic agent, can't be applicable to this purpose.

In addition; a kind of cleaning method is disclosed in the patent documentation 3; the wafer surface that its film that utilization is comprised silicon by oxidation etc. has formed the concaveconvex shape pattern is carried out surface modification; use water soluble surfactant active or silane coupler to form the water repellency diaphragm on this surface; reduce capillary force, prevent collapsing of pattern.

In addition, disclose following technology in the patent documentation 4,5, comprised with N by use, the silylation agent headed by the N-dimethylamino trimethyl silane and the treatment fluid of solvent carry out hydrophobization to be handled, thereby prevents that pattern from toppling over.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2008-198958 communique

Patent documentation 2: Japanese kokai publication hei 5-299336 communique

Patent documentation 3: No. 4403202 communique of Japan Patent

Patent documentation 4: TOHKEMY 2010-129932 communique

Patent documentation 5: the international brochure that discloses No. 10/47196

Summary of the invention

The problem that invention will solve

The present invention relates to the cleaning technique of substrate (wafer), in semiconductor device manufacturing etc., this cleaning technique with improve especially fine and circuit pattern change that depth-width ratio is high the fabrication yield of device be purpose; The present invention be more particularly directed to the water repellency diaphragm and form with chemical solution etc., to bring out the matting that relief pattern that the surface has the wafer of relief pattern topples over easily be purpose to this chemical solution to improve.

Though use the surface to have the wafer of element silicon usually as aforementioned wafer so far, but the variation along with pattern, bring into use the surface to have the wafer of the element (below, be designated as " metal series elements " sometimes) of titanium, tungsten, aluminium, copper, tin, tantalum and ruthenium and so on.But; the wafer that has the aforementioned metal series elements such as the surface; comprising under the situation of wafer of material that the surface do not exist enough reactive functional groups, for example silanol group; even if use treatment fluid and the processing method of patent documentation 3 to 5 records also can't form the water repellency diaphragm that prevents pattern collapse, therefore have the problem that can't prevent pattern collapse.

Problem of the present invention is to provide the following diaphragm that is used to form the water repellency diaphragm to form and uses chemical solution; its by the recess surface that is formed with relief pattern and this relief pattern on the surface have at least a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium wafer (below; sometimes be designated as " metal is wafer " or only be designated as " wafer ") recess surface at least form the water repellency diaphragm; reduce remaining in the liquid of this recess and the interaction of this recess surface, bring out the matting that pattern topples over easily thereby improve.

For the scheme of dealing with problems

Pattern topples over and takes place when gas-liquid interface is by pattern when carrying out drying after with the cleaning fluid clean wafers.Think that its reason is, the raffinate difference in height of cleaning fluid between the high part of the depth-width ratio of pattern and low part, occurs, make the capillary force that acts on pattern produce difference thus.

Therefore, if capillary force is diminished, can expect that then the difference of the capillary force that caused by the difference of raffinate height reduces, pattern be toppled over solved.The size of capillary force, then can be expected to reduce capillary force if γ or cos θ in this formula are diminished for the absolute value of the P that obtained by formula shown below.

P=2×γ×cosθ/S

(in the formula, γ is the surface tension that remains in the liquid of recess, and θ is the contact angle that recess surface and the liquid that remains in recess form, and S is the width of recess.)

Among the present invention; when the liquid that residues in recess after forming the water repellency diaphragm is removed from recess, when namely being dried, be formed with aforementioned diaphragm in the recess surface at least of aforementioned relief pattern; therefore the capillary force that acts on this recess diminishes, and is difficult to produce pattern and topples over.In addition, aforementioned diaphragm is removed behind drying process.

Water repellency diaphragm formation chemical solution of the present invention (below; sometimes be designated as " diaphragm forms and uses chemical solution " or only be designated as " chemical solution ") be characterised in that; its for comprise following water repellency diaphragm form agent (below; sometimes only be designated as " diaphragm formation agent ") and the chemical solution of solvent; described water repellency diaphragm forms agent and has titanium for the recess surface that is formed with relief pattern and this relief pattern on the surface; tungsten; aluminium; copper; tin; after the matting of the wafer of at least a kind of element in tantalum and the ruthenium and before the drying process recess surface at least form the water repellency diaphragm (below; sometimes only be designated as " diaphragm "), this water repellency diaphragm forms the compound that agent is following general formula [1] expression.

(in the formula [1], R ¹Be that the optional carbon number that is replaced by fluorine element of part or all protium is 1 to 18 1 valency alkyl.R ²Be to comprise the 1 valency organic group that the optional carbon number that is replaced by fluorine element of part or all protium is 1 to 18 alkyl separately independently of each other.A is 0 to 2 integer.)

Forming agent by the diaphragm that uses aforementioned formula [1] expression, can be the formation of the recess surface at least water repellency diaphragm of wafer in aforementioned metal.Form agent about this diaphragm, P-OH base and/or P=O base (below, be designated as " sense portion " sometimes) material that comprises the aforementioned metal series elements is had compatibility.Herein; thereby having compatibility refers to that Van der Waals force or electrostatic interaction etc. form at the aforementioned material surface that comprises the metal series elements and aforementioned diaphragm to have an effect between the sense portion of agent and makes its absorption; and/or the sense portion reaction of this material surface and aforementioned diaphragm formation agent, thereby form chemical bond absorption.In addition, R ¹Be that diaphragm forms the hydrophobic portion of agent, this diaphragm forms agent and is adsorbed in metal when being the aforementioned metal series elements of wafer, and this hydrophobic portion is arranged laterally from this wafer surface, and it is water repellency that its result can make this wafer surface.

In addition, aforementioned diaphragm forms the compound that agent is preferably following general formula [2] expression.

(in the formula [2], R ³Be that the optional carbon number that is replaced by fluorine element of part or all protium is 1 to 18 1 valency alkyl.)

Be wafer as aforementioned metal, can enumerate the metal that recess surface at relief pattern has at least a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium is wafer, be preferably have titanium, the metal of at least a kind of element in tungsten, aluminium and the ruthenium is wafer, being preferably the metal with titanium elements especially is wafer.Metal is that wafer is under the situation of wafer with element silicon of recess surface at relief pattern; because there are many silanol groups (SiOH yl) in the surface; this silanol group becomes the reaction site with silane coupler, therefore forms the water repellency diaphragm in recess surface easily.On the other hand, metal is in the wafer, and it is few to be equivalent to the such reaction site of silanol group on the surface, is difficult to form diaphragm with the such compound of silane coupler.In addition, among the present invention, the wafer that the surface has a relief pattern means the wafer by the state after the surface forms relief pattern such as etching or impression.In addition, also can implement other processing such as metal line to aforementioned wafer, as long as there is relief pattern in its surface, just can be used as object.

Form for diaphragm of the present invention and to use chemical solution, in aforementioned metal is the matting of wafer, cleaning fluid is replaced into this chemical solution and uses.In addition, the chemical solution of aforementioned displacement also can be replaced into other cleaning fluid.

In addition; water repellency diaphragm of the present invention is characterised in that; it has for the recess surface that is formed with relief pattern and this relief pattern on the surface after the matting of wafer of a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium and before the drying process at least; aforementioned diaphragm formation is remained in this recess at least with chemical solution; thereby at the water repellency diaphragm of recess surface formation, this water repellency diaphragm is to be formed by the compound that the aforementioned formula [1] that forms agent as the water repellency diaphragm is represented at least.Need to prove that aforementioned water repellency diaphragm can comprise with the compound of aforementioned formula [1] the expression reactant as main component.

As aforementioned, after matting, cleaning fluid is replaced into diaphragm and forms and use chemical solution, the recess at least of relief pattern maintain this chemical solution during in, form aforementioned diaphragm in the recess surface at least of this relief pattern.Diaphragm of the present invention is not to form continuously, in addition, is not to be formed uniformly yet, but in order to give more excellent water repellency, more preferably continuously and be formed uniformly.

In the present invention, diaphragm refers to by being formed at film that wafer surface reduces the wetability of this wafer surface, namely giving the film of water repellency.In the present invention, water repellency refers to by the surface that reduces article surface the interaction at (interface) between water, other liquid and this article surface is reduced, and for example makes reductions such as hydrogen bond, molecular separating force.Particularly reduce greatly with respect to the interactional effect of water, even with respect to the mixed liquor of water and the liquid except water, the liquid except water, also have and reduce interactional effect.By reducing this interaction, can increase liquid with respect to the contact angle of article surface.

In addition, the cleaning method of wafer of the present invention is characterised in that, it is the cleaning method that the surperficial recess surface that is formed with relief pattern and this relief pattern has the wafer of at least a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium, and this method has following operation at least:

Recess at least at relief pattern keeps diaphragm formation to form operation with the diaphragm of chemical solution;

The drying process of liquid being removed from relief pattern by drying;

Remove the film of diaphragm and remove operation,

It is to comprise the chemical solution that forms agent for the water repellency diaphragm that forms the water repellency diaphragm on aforementioned recess surface at least that aforementioned diaphragm forms with chemical solution, and aforementioned water repellency diaphragm is to be formed by the compound that the aforementioned formula [1] that forms agent as the water repellency diaphragm is represented.

The effect of invention

Owing to utilize diaphragm of the present invention to form the water repellency excellence of the diaphragm that forms with chemical solution; so the recess surface that is formed with relief pattern and this relief pattern for the surface has for the wafer of a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium at least; the interaction of the liquid that remains in this recess and this recess surface is reduced, and then demonstrate the effect that prevents that pattern from toppling over.When using this chemical solution, the matting that the surface has in the manufacture method of wafer of relief pattern improves, and production capacity can not reduce.Therefore, use diaphragm of the present invention to form the productivity ratio height of manufacture method that the surface of carrying out with chemical solution has the wafer of relief pattern.

Diaphragm of the present invention form with chemical solution can also tackle that prediction will more be increased from now on, for example have the relief pattern of the depth-width ratio more than 7, can make the semiconductor device production cost reduction of more densification.And can be not in the past device is not carried out big change and tackles, its result can be applied to the manufacturing of various semiconductor device.

Description of drawings

Fig. 1 is the schematic perspective view of the surface being made the wafer 1 of the face with relief pattern 2.

Fig. 2 is the schematic diagram that the part of the a-a ' section among Fig. 1 is shown.

Fig. 3 maintains the schematic diagram that diaphragm forms the state of using chemical solution 8 at matting center dant 4.

Fig. 4 is formed with the schematic diagram that maintains the state of liquid in the recess 4 of diaphragm.

Embodiment

Be wafer as metal, can enumerate with silicon wafer, by comprising silicon and/or silicon dioxide (SiO ₂) the wafer that constitutes of multiple composition, silicon carbide wafer, sapphire wafer, the surface titanium of various kinds of compound semiconductors wafer and plastic substrate etc., titanium nitride, titanium oxide etc. comprise the material of titanium elements, perhaps tungsten, tungsten oxides etc. comprise the material of W elements, aluminium or aluminium oxide etc. comprise the material of aluminium element, copper or cupric oxide etc. comprise the material of copper, tin or tin oxide etc. comprise the material of tin element, tantalum nitride or tantalum oxide etc. comprise the material of tantalum element, perhaps ruthenium or ruthenium-oxide etc. comprise layer wafer that covers of the material of ruthenium element; Perhaps form multilayer film at wafer, wherein at least 1 layer is the wafer etc. of layer that comprises the material of aforementioned metal series elements, and above-mentioned relief pattern forms operation the layer of the layer that contains the material that comprises the aforementioned metal series elements is carried out.Comprise also that in addition at least a portion on the surface of this relief pattern is the wafer with material of at least a kind of element in the aforementioned metal series elements when forming relief pattern.

Use diaphragm of the present invention to form with before the surface treatment of chemical solution in enforcement, how can experience following cited pretreatment procedure usually:

With wafer surface make the face with relief pattern pretreatment procedure 1,

Pretreatment procedure 2 and that use the water system cleaning fluid that wafer surface is cleaned

Aforementioned water system cleaning fluid is replaced into the pretreatment procedure 3 of the cleaning fluid A different with this water system cleaning fluid (below, only be designated as " cleaning fluid A " sometimes).

Need to prove that any one in pretreatment procedure 2 or the pretreatment procedure 3 also can be omitted sometimes.

In aforementioned pretreatment procedure 1, pattern formation method is: at first, at this wafer surface painting erosion resistant agent, across Etching mask resist is exposed then, resist or the unexposed resist that has exposed removed in etching, thereby makes the resist with desirable relief pattern.In addition, will have the molding of pattern by being pressed in the resist that also can obtain to have relief pattern on the resist.Then, wafer is carried out etching.At this moment, the recessed part of corrosion-resisting pattern is selectively etched.At last, if peel off resist, then obtain to have the wafer of relief pattern.

By above-mentioned pretreatment procedure 1, obtain the wafer that recess surface that the surface is formed with relief pattern and this relief pattern has at least a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium.

Example as the water system cleaning fluid that uses in the aforementioned pretreatment procedure 2, can enumerate water or in water, mix the water system cleaning fluid of at least a kind the aqueous solution (for example, the containing ratio of water is more than the 10 quality %) in organic solvent, hydrogen peroxide, ozone, acid, alkali, the surfactant.

In addition, in pretreatment procedure 2, can carry out more than 2 times to the displacement of water system cleaning fluid.The water system cleaning fluid that use this moment can be distinguished difference.

In aforementioned pretreatment procedure 2 with the water system cleaning fluid carry out the surface cleaning after, if directly be replaced into behind the water by removal water such as dryings by removals water system cleaning fluid such as drying or with the water system cleaning fluid, then the width of recess depth-width ratio little, protuberance is big, is easy to produce pattern and topples over.This relief pattern defines as recording and narrating among Fig. 1 and Fig. 2.Fig. 1 illustrates an example of schematic perspective view of the surface being made the wafer 1 of the face with relief pattern 2, and Fig. 2 illustrates the part of the a-a ' section among Fig. 1.The width 5 of recess is as shown in Figure 2 by protuberance 3 time interval with protuberance 3, the value representation that the depth-width ratio of protuberance is obtained divided by the width 7 of protuberance by the height 6 of protuberance.Pattern in the matting topple over easily the width of recess below the 70nm particularly below the 45nm, depth-width ratio more than 4 particularly in 6 generations when above.

The cleaning fluid A that uses in the pretreatment procedure 3 represent organic solvent, this organic solvent with the mixture of water system cleaning fluid, in them, mixed at least a kind cleaning fluid in acid, alkali, the surfactant.In addition, preferably carry out following operation (diaphragm formation operation): form and use chemical solution by this cleaning fluid A being replaced into diaphragm of the present invention, keep this diaphragm formation chemical solution at the recess at least of relief pattern.

Among the present invention, as long as the recess at least of the relief pattern of wafer can keep aforementioned chemical solution, cleaning fluid, then the cleaning way of this wafer is not particularly limited.As the cleaning way of wafer, can enumerate: cleaning with rotation is the single chip mode of representative, makes wafer keep substantially flatly rotating and liquid is supplied near the pivot blocks of ground clean wafers; Batch mode, dipping multi-disc wafer cleans in rinse bath.Need to prove, as this chemical solution during to the recess at least of the relief pattern of wafer, the form of cleaning fluid with aforementioned chemical solution, cleaning solution supplying, as long as be that liquid then is not particularly limited when being held in this recess, for example, liquid, steam etc. are arranged.

As the representative examples of organic of one of preference of aforementioned cleaning fluid A, can enumerate hydro carbons, ester class, ethers, ketone, halogen-containing element solvent, sulfoxide series solvent, lactone series solvent, carbonic ester series solvent, alcohols, the derivative of polyalcohol, nitrogenous element solvent etc.

Example as aforementioned hydro carbons, toluene is arranged, benzene, dimethylbenzene, hexane, heptane, octane etc., example as aforementioned ester class, ethyl acetate is arranged, propyl acetate, butyl acetate, ethyl acetoacetate etc., example as aforementioned ethers, Anaesthetie Ether is arranged, dipropyl ether, dibutyl ethers, oxolane diox etc., example as aforementioned ketone, acetone is arranged, acetylacetone,2,4-pentanedione, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone etc., example as aforementioned halogen-containing element solvent, PFO is arranged, Perfluorononane, Decafluorocyclopentane, the perfluor cyclohexane, perfluocarbons such as phenyl-hexafluoride, 1,1,1,3, the 3-3-pentafluorobutane, Octafluorocyclopentane, 2,3-dihydro Decafluoropentane, ZEOROLA-H hydrogen fluorohydrocarbons such as (ZEON CORPORATION manufacturings), methyl perfluor isobutyl ether, the methyl perfluorobutyl ether, the ethyl perfluorobutyl ether, ethyl perfluor isobutyl ether, ASAHIKLIN AE-3000 (manufacturing of Asahi Glass company), Novec-7100, Novec-7200, Novec7300, Novec7600 hydrogen fluorine ethers such as (being 3M company make), chlorocarbons such as tetrachloromethane, hydrogen chlorocarbons such as chloroform, CFC such as dicholorodifluoromethane, 1,1-two chloro-2,2,3,3, the 3-pentafluoropropane, 1,3-two chloro-1,1,2,2, the 3-pentafluoropropane, 1-chloro-3,3, the 3-trifluoro propene, 1,2-two chloro-3,3, HCFCs such as 3-trifluoro propene, perfluor ether, PFPE etc., example as aforementioned sulfoxide series solvent, dimethyl sulfoxide (DMSO) etc. is arranged, example as aforementioned lactone series solvent, gamma-butyrolacton is arranged, gamma-valerolactone, γ-Ji Neizhi, γ-Geng Neizhi, γ-Xin Neizhi, nonyl lactone, γ-decalactone, gamma-undecalactone, γ-dodecalactone, δ-Wu Neizhi, δ-caprolactone, δ-Xin Neizhi, δ-nonalactone, δ-Gui Neizhi, delta-undeca lactone, δ-Shi Erneizhi, 6-caprolactone etc., example as aforementioned carbonic ester series solvent, dimethyl carbonate is arranged, methyl ethyl carbonate, diethyl carbonate, propylene carbonate etc., example as alcohols, methyl alcohol is arranged, ethanol, propyl alcohol, butanols, ethylene glycol, diethylene glycol, 1, the 2-propylene glycol, 1, ammediol, dipropylene glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, triethylene glycol, tripropylene glycol, TEG, four propylene glycol, glycerine etc., example as the derivative of aforementioned polyalcohol, the glycol monomethyl methyl ether is arranged, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, the diethylene glycol single-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, triethylene glycol list propyl ether, the triethylene glycol single-butyl ether, the TEG monomethyl ether, TEG list ethylether, TEG list propyl ether, the TEG single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list propyl ether, the dipropylene glycol single-butyl ether, the tripropylene glycol monomethyl ether, tripropylene glycol list ethylether, tripropylene glycol list propyl ether, the tripropylene glycol single-butyl ether, four propylene glycol monomethyl ether, the butanediol monomethyl ether, ethylene glycol dimethyl ether, the ethylene glycol bisthioglycolate ethylether, the ethylene glycol bisthioglycolate butyl ether, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, the ethylene glycol monobutyl ether acetic acid esters, ethylene acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, the diethylene glycol dibutyl ethers, the diethylene glycol monomethyl ether acetic acid esters, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, the diethylene glycol diacetate esters, the triethylene glycol dimethyl ether, the triethylene glycol Anaesthetie Ether, the triethylene glycol dibutyl ethers, triethylene glycol butyl methyl ether, the triethylene glycol monomethyl ether acetate, triethylene glycol list ethylether acetic acid esters, triethylene glycol single-butyl ether acetic acid esters, the triethylene glycol diacetate esters, the TEG dimethyl ether, the TEG Anaesthetie Ether, the TEG dibutyl ethers, the TEG monomethyl ether acetate, TEG list ethylether acetic acid esters, TEG single-butyl ether acetic acid esters, the TEG diacetate esters, the propylene glycol dimethyl ether, the propylene glycol Anaesthetie Ether, the propylene glycol dibutyl ethers, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol single-butyl ether acetic acid esters, propylene-glycol diacetate, the dipropylene glycol dimethyl ether, dipropylene glycol methyl-propyl ether, the dipropylene glycol Anaesthetie Ether, the dipropylene glycol dibutyl ethers, the dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters, the dipropylene glycol diacetate esters, the tripropylene glycol dimethyl ether, the tripropylene glycol Anaesthetie Ether, the tripropylene glycol dibutyl ethers, the tripropylene glycol monomethyl ether acetate, tripropylene glycol list ethylether acetic acid esters, tripropylene glycol single-butyl ether acetic acid esters, the tripropylene glycol diacetate esters, four propylene glycol dimethyl ethers, four propylene glycol monomethyl ether, four propylene-glycol diacetates, the butanediol dimethyl ether, the butanediol monomethyl ether acetate, the butanediol diacetate esters, glycerol triacetate etc., example as nitrogenous element solvent, formamide is arranged, N, dinethylformamide, N, the N-dimethylacetylamide, the N-N-methyl-2-2-pyrrolidone N-, diethylamine, triethylamine, pyridine etc.

Need to prove that from the viewpoint of purity, aforementioned cleaning fluid A is preferably the mixed liquor of organic solvent, water and organic solvent.Need to prove, if this organic solvent comprises water-miscible organic solvent (solubility in water 100 mass parts is more than 5 mass parts), then easily by the displacement of water system cleaning fluid, thereby preferred.

In addition, in pretreatment procedure 3, can carry out more than 2 times to the displacement of cleaning fluid A.That is, after the water system cleaning fluid that can use is replaced into the 1st kind of cleaning fluid A, be replaced into the multiple cleaning fluid A different with this cleaning fluid A successively in by pretreatment procedure 2, be replaced into aforementioned diaphragm formation chemical solution then.

In addition, the water system cleaning fluid direct replacement of using in can be by pretreatment procedure 2 is that aforementioned diaphragm forms under the usefulness situation of chemical solution, can omit the displacement (pretreatment procedure 3) that utilizes aforementioned cleaning fluid A.

Fig. 3 shows diaphragm formation operation center dant 4 and maintains the schematic diagram that diaphragm forms the state of using chemical solution 8.The wafer of the schematic diagram of Fig. 3 illustrates the part of the a-a ' section of Fig. 1.At this moment, form diaphragm by the surface at recess 4, thereby should be refused aquation in the surface.

Need to prove that what the enough chemical solutions of the present invention of energy formed diaphragm is surface in the aforementioned relief pattern, that have the material part of at least a kind of element in the metal series elements.Therefore, aforementioned diaphragm can be the part formation of the recess surface at least of wafer in aforementioned metal.In addition, even for the wafer that is made of a plurality of compositions that comprise the material with at least a kind of element in the aforementioned metal series elements, the surface of the material of at least a kind of element that also can be in having the aforementioned metal series elements forms aforementioned diaphragm.As this wafer that is constituted by a plurality of compositions, also comprise: the material with at least a kind of element in the metal series elements is formed at the wafer of the part of recess surface at least, perhaps, when having formed relief pattern, the part of recess surface becomes the wafer of the material with at least a kind of element in the metal series elements at least.

Need to prove; diaphragm of the present invention forms with chemical solution owing to have this surface of the article of titanium elements easily on the surface and forms excellent water repellency diaphragm, therefore aforementioned wafer more preferably the surperficial recess surface that is formed with relief pattern and this relief pattern have the wafer of titanium elements.

It is to comprise the chemical solution that following diaphragm forms agent and solvent that aforementioned diaphragm forms with chemical solution; described diaphragm forms agent and is used for after aforementioned metal is the matting of wafer and forms diaphragm in recess surface at least before the drying process, and it is the compound that following general formula [1] is represented that this water repellency diaphragm forms agent.

The R of aforementioned formula [1] ²In the alkyl that comprises for example can enumerate group that alkyl, alkylidene or their part or all protium replaced by fluorine element etc.

In addition, aforementioned R ²Be preferably-OR ⁴(R ⁴Be that carbon number is 1 to 18 alkyl).In addition, R ⁴Carbon number be 1～8, particularly 1～4 o'clock, can give more excellent water repellency, thereby preferred.In addition, R ⁴Be preferably straight chained alkyl.

As the compound of aforementioned formula [1], for example, can enumerate CH ₃P (O) (OH) ₂, C ₂H ₅P (O) (OH) ₂, C ₃H ₇P (O) (OH) ₂, C ₄H ₉P (O) (OH) ₂, C ₅H ₁₁P (O) (OH) ₂, C ₆H ₁₃P (O) (OH) ₂, C ₇H ₁₅P (O) (OH) ₂, C ₈H ₁₇P (O) (OH) ₂, C ₉H ₁₉P (O) (OH) ₂, C ₁₀H ₂₁P (O) (OH) ₂, C ₁₁H ₂₃P (O) (OH) ₂, C ₁₂H ₂₅P (O) (OH) ₂, C ₁₃H ₂₇P (O) (OH) ₂, C ₁₄H ₂₉P (O) (OH) ₂, C ₁₅H ₃₁P (O) (OH) ₂, C ₁₆H ₃₃P (O) (OH) ₂, C ₁₇H ₃₅P (O) (OH) ₂, C ₁₈H ₃₇P (O) (OH) ₂, C ₆H ₅P (O) (OH) ₂, CF ₃P (O) (OH) ₂, C ₂F ₅P (O) (OH) ₂, C ₃F ₇P (O) (OH) ₂, C ₄F ₉P (O) (OH) ₂, C ₅F ₁₁P (O) (OH) ₂, C ₆F ₁₃P (O) (OH) ₂, C ₇F ₁₅P (O) (OH) ₂, C ₈F ₁₇P (O) (OH) ₂, CF ₃C ₂H ₄P (O) (OH) ₂, C ₂F ₅C ₂H ₄P (O) (OH) ₂, C ₃F ₇C ₂H ₄P (O) (OH) ₂, C ₄F ₉C ₂H ₄P (O) (OH) ₂, C ₅F ₁₁C ₂H ₄P (O) (OH) ₂, C ₆F ₁₃C ₂H ₄P (O) (OH) ₂, C ₇F ₁₅C ₂H ₄P (O) (OH) ₂, C ₈F ₁₇C ₂H ₄P (O) (OH) ₂, or with above-claimed cpd-P (O) (OH) ₂Base replaces with-(OH) OCH of P (O) ₃Base ,-(OH) OC of P (O) ₂H ₅Base ,-P (O) (OCH ₃) ₂Base ,-P (O) (OC ₂H ₅) ₂The compound of base etc.

In addition, aforementioned diaphragm is formed agent, in order to give more excellent water repellency, thereby the compound that a of preferred aforementioned formula [1] is 1 or 2, further preferred a is 2 following general formula [2] expression.

The R of aforementioned formula [1], [2] ¹, R ³The protium that for example can enumerate alkyl, phenyl, phenyl is substituted by group that part or all protiums of group, naphthyl and these alkyl of alkyl replaced by fluorine element etc.

In addition, the R of aforementioned formula [1], [2] ¹, R ³Carbon number be 2～16, particularly 4～14 and then be 6～14 o'clock, can give more excellent water repellency, thereby preferred.In addition, the optional alkyl that is replaced by fluorine element of aforementioned part or all protium is preferably alkyl, is preferably straight chained alkyl especially.If aforementioned alkyl is straight chained alkyl, then when forming diaphragm, aforementioned diaphragm forms the hydrophobic portion of agent and arranges towards vertical direction easily with respect to the surface of this diaphragm, thus water repellency to give effect higher, so more preferably.In addition, in order to give more excellent water repellency, thereby the R of aforementioned formula [1], [2] ¹, R ³Be that part or all protium is advisable by the alkyl that fluorine element replaces.

In addition, aforementioned diaphragm forms agent and can exist with the form of the salt of aforementioned formula [1], [2].As this salt, ammonium salt or amine salt etc. are arranged.

In addition, diaphragm forms with the concentration of the formation of the diaphragm in chemical solution agent and is preferably 0.0005～2 quality % with respect to the total amount 100 quality % of this chemical solution.When being lower than 0.0005 quality %, having water repellency and give effect inadequate tendency, if surpass 2 quality %, then have the tendency that is difficult to be dissolved in organic solvent.More preferably 0.001～1 quality %, be preferably 0.0015～0.8 quality % especially.

Form with the solvent that uses in the chemical solution the suitable mixed liquor that makes water, organic solvent, water and organic solvent as diaphragm.As this organic solvent, for example, suitable hydro carbons, ester class, ethers, ketone, halogen-containing element solvent, sulfoxide series solvent, lactone series solvent, carbonic ester series solvent, alcohols, the derivative of polyalcohol, nitrogenous element solvent or their mixed liquor of using.

As the concrete example of above-mentioned organic solvent, can enumerate with aforementioned cleaning fluid A in the same organic solvent of the organic solvent that uses.

In addition, if part or all of aforementioned solvents used non-flame properties solvent, then diaphragm formation is that noninflammability or flash-point improve with chemical solution, thereby the danger of this chemical solution is reduced, thereby preferred.Mostly halogen-containing element solvent is non-flame properties, and non-flame properties halogen-containing element solvent can suit to use as the noninflammability organic solvent.In addition, water also can suit to use as the noninflammability solvent.

In addition, if use flash-point to surpass 70 ℃ solvent as aforementioned solvents, the viewpoint of the fail safe on the Fire Prevention Law is preferred.

In addition, according to " being in harmonious proportion system about the whole world of the classification of chemicals and expression; GHS ", be that solvent below 93 ℃ is defined as " flammable liquid " with flash-point.Therefore; even if be not the noninflammability solvent, if use the solvent of flash-point above 93 ℃ as aforementioned solvents, then aforementioned diaphragm formation uses the flash-point of chemical solution also easily above 93 ℃; this chemical solution is difficult to meet " flammable liquid ", and is therefore further preferred from the viewpoint of fail safe.

In addition; lactone series solvent, carbonic ester series solvent, molecular weight are big or have the alcohols of 2 above OH bases, the derivative of polyalcohol mostly is the high material of flash-point; therefore if these are used for solvent, then can reduce diaphragm and form the danger of using chemical solution, thus preferred.Viewpoint from above-mentioned fail safe, specifically more preferably flash-point is surpassed 70 ℃ gamma-butyrolacton, gamma-valerolactone, γ-Ji Neizhi, γ-Geng Neizhi, γ-Xin Neizhi, nonyl lactone, γ-decalactone, gamma-undecalactone, γ-dodecalactone, δ-Wu Neizhi, δ-caprolactone, δ-Xin Neizhi, δ-nonalactone, δ-Gui Neizhi, delta-undeca lactone, δ-Shi Erneizhi, 6-caprolactone, propylene carbonate, enanthol, octanol, ethylene glycol, diethylene glycol, 1, the 2-propylene glycol, 1, ammediol, dipropylene glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, triethylene glycol, tripropylene glycol, TEG, four propylene glycol, glycerine, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, the diethylene glycol single-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, triethylene glycol list propyl ether, the triethylene glycol single-butyl ether, the TEG monomethyl ether, TEG list ethylether, TEG list propyl ether, the TEG single-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list propyl ether, the dipropylene glycol single-butyl ether, the tripropylene glycol monomethyl ether, tripropylene glycol list ethylether, tripropylene glycol list propyl ether, the tripropylene glycol single-butyl ether, four propylene glycol monomethyl ether, the ethylene glycol bisthioglycolate butyl ether, the ethylene glycol monobutyl ether acetic acid esters, ethylene acetate, diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, the diethylene glycol dibutyl ethers, the diethylene glycol monomethyl ether acetic acid esters, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, the diethylene glycol diacetate esters, the triethylene glycol dimethyl ether, the triethylene glycol Anaesthetie Ether, the triethylene glycol dibutyl ethers, triethylene glycol butyl methyl ether, the triethylene glycol monomethyl ether acetate, triethylene glycol list ethylether acetic acid esters, triethylene glycol single-butyl ether acetic acid esters, the triethylene glycol diacetate esters, the TEG dimethyl ether, the TEG Anaesthetie Ether, the TEG dibutyl ethers, the TEG monomethyl ether acetate, TEG list ethylether acetic acid esters, TEG single-butyl ether acetic acid esters, the TEG diacetate esters, propylene-glycol diacetate, dipropylene glycol methyl-propyl ether, the dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters, the dipropylene glycol diacetate esters, the tripropylene glycol dimethyl ether, the tripropylene glycol Anaesthetie Ether, the tripropylene glycol dibutyl ethers, the tripropylene glycol monomethyl ether acetate, tripropylene glycol list ethylether acetic acid esters, tripropylene glycol single-butyl ether acetic acid esters, the tripropylene glycol diacetate esters, four propylene glycol dimethyl ethers, four propylene glycol monomethyl ether, four propylene-glycol diacetates, the butanediol diacetate esters, glycerol triacetates etc. use as aforementioned solvents, further preferably flash-point is surpassed 93 ℃ gamma-butyrolacton, γ-Ji Neizhi, γ-Geng Neizhi, γ-Xin Neizhi, nonyl lactone, γ-decalactone, gamma-undecalactone, γ-dodecalactone, δ-Wu Neizhi, δ-caprolactone, δ-Xin Neizhi, δ-nonalactone, δ-Gui Neizhi, delta-undeca lactone, δ-Shi Erneizhi, 6-caprolactone, propylene carbonate, ethylene glycol, diethylene glycol, 1, the 2-propylene glycol, 1, ammediol, dipropylene glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, TEG, four propylene glycol, glycerine, diethylene glycol monomethyl ether, diethylene glycol list propyl ether, the diethylene glycol single-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, triethylene glycol list propyl ether, the triethylene glycol single-butyl ether, the TEG monomethyl ether, TEG list ethylether, TEG list propyl ether, the TEG single-butyl ether, dipropylene glycol list propyl ether, the dipropylene glycol single-butyl ether, the tripropylene glycol monomethyl ether, tripropylene glycol list ethylether, tripropylene glycol list propyl ether, the tripropylene glycol single-butyl ether, four propylene glycol monomethyl ether, ethylene acetate, diethylene glycol butyl methyl ether, the diethylene glycol dibutyl ethers, the diethylene glycol diacetate esters, the diethylene glycol monomethyl ether acetic acid esters, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, the triethylene glycol dimethyl ether, the triethylene glycol Anaesthetie Ether, the triethylene glycol dibutyl ethers, triethylene glycol butyl methyl ether, the triethylene glycol monomethyl ether acetate, triethylene glycol list ethylether acetic acid esters, triethylene glycol single-butyl ether acetic acid esters, the triethylene glycol diacetate esters, the TEG dimethyl ether, the TEG Anaesthetie Ether, the TEG dibutyl ethers, the TEG monomethyl ether acetate, TEG list ethylether acetic acid esters, TEG single-butyl ether acetic acid esters, the TEG diacetate esters, propylene-glycol diacetate, the dipropylene glycol diacetate esters, the dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters, the tripropylene glycol dimethyl ether, the tripropylene glycol Anaesthetie Ether, the tripropylene glycol dibutyl ethers, the tripropylene glycol monomethyl ether acetate, tripropylene glycol list ethylether acetic acid esters, tripropylene glycol single-butyl ether acetic acid esters, the tripropylene glycol diacetate esters, four propylene glycol dimethyl ethers, four propylene glycol monomethyl ether, four propylene-glycol diacetates, the butanediol diacetate esters, glycerol triacetates etc. use as aforementioned solvents.

In addition, because the reason that can give more excellent water repellency, aforementioned solvents is preferably material, water or their mixed liquor that does not have hydroxyl in the derivative of hydro carbons, ester class, ethers, ketone, lactone series solvent, carbonic ester series solvent, polyalcohol.In addition, as if consideration and cleaning fluid, the particularly displacement of water system cleaning fluid, be preferably derivative, water or their mixed liquor of the polyalcohol with hydroxyl.Need to prove, dissolve in a large number in order to make aforementioned diaphragm form agent, can in aforementioned solvents, contain alcohols.Need to prove that the concentration of this alcohols under this situation forms with respect to diaphragm and is preferably below the 10 quality % with chemical solution 100 quality %, is preferably especially below the 5 quality %, more preferably below the 3 quality %.

In addition, form diaphragm in order to promote aforementioned diaphragm to form agent, can in diaphragm forms with chemical solution, add catalyst.The addition of catalyst is preferably 0.01～50 quality % with respect to the total amount 100 quality % that diaphragm forms agent.

When the raising diaphragm forms with the temperature of chemical solution, in shorter time, form aforementioned diaphragm easily.The temperature that forms easily the diaphragm of homogeneous is more than 10 ℃ and is lower than the boiling point of this chemical solution, especially preferably remains on more than 15 ℃ and hangs down than the boiling point of this chemical solution below 10 ℃ the temperature.The temperature of aforementioned chemical solution preferably also keeps this temperature when being held in the recess at least of relief pattern.Need to prove that the boiling point of this chemical solution refers to measure by quality ratio the boiling point of maximum compositions in the composition that this water repellency chemical solution contains.

After aforementioned diaphragm forms operation; can be replaced at the aforementioned chemical solution that the recess at least of this relief pattern is residual the cleaning fluid different with this chemical solution (below; sometimes be designated as " cleaning fluid B ") (below, be designated as " back matting " sometimes) after, transfer to drying process.As the example of aforementioned cleaning fluid B, can enumerate the mixture of water system cleaning fluid, organic solvent, aforementioned water system cleaning fluid and organic solvent or in them, mixed at least a kind material in acid, alkali, the surfactant and in them, contain diaphragm and form with the material of the diaphragm formation agent of using in the chemical solution etc. to be lower than concentration that diaphragm in this chemical solution forms the concentration of agent.From removing the viewpoint of particle and metal impurities, aforementioned cleaning fluid B is the mixture of water, organic solvent or aforementioned water and organic solvent more preferably.

In addition, in the matting of back, can carry out more than 2 times to the displacement of aforementioned cleaning fluid B.That is, can formed by diaphragm be replaced into the 1st kind of cleaning fluid B with chemical solution after, be replaced into successively and the 1st kind of multiple cleaning fluid B that cleaning fluid B is different, transfer to drying process then.

As the representative examples of organic of one of preference of aforementioned cleaning fluid B, can enumerate hydro carbons, ester class, ethers, ketone, halogen-containing element solvent, sulfoxide series solvent, alcohols, the derivative of polyalcohol, nitrogenous element solvent etc.

As the concrete example of above-mentioned organic solvent, can enumerate with aforementioned cleaning fluid A, aforementioned diaphragm and form with the same organic solvent of the organic solvent that uses in the chemical solution.

In addition, utilize diaphragm that chemical solution of the present invention forms in wafer surface if with an organic solvent as aforementioned cleaning fluid B, then have the tendency that water repellency can not reduce because of aforementioned back matting basically.

Form the illustrating in Fig. 4 of situation that the recess 4 of refusing aquation with chemical solution maintains liquid by diaphragm.The wafer of the schematic diagram of Fig. 4 illustrates the part of the a-a ' section of Fig. 1.The relief pattern surface forms diaphragm 10 by aforementioned chemical solution and refuses aquation.And this diaphragm 10 still is maintained at wafer surface when removing liquid 9 from relief pattern.

Form when forming diaphragm 10 with chemical solution by diaphragm in the recess surface at least of the relief pattern of wafer, if the contact angle when this surface of supposition maintains water is 50～130 °, is difficult to that then pattern takes place and topples over, thereby preferably.Contact angle is more more little near 90 ° of capillary forces that then act on this recess, is difficult to that more pattern takes place and topples over, and therefore more preferably 60～120 °, is preferably 65～115 ° especially.In addition, capillary force is preferably 2.1MN/m ²Below.If this capillary force is 2.1MN/m ²Below, be difficult to that then pattern takes place and topple over, thus preferred.In addition, if this capillary force diminishes, be difficult to more that then pattern takes place and topple over, so this capillary force 1.6MN/m more preferably ²Below, be preferably 1.4MN/m especially ²Below.In addition, it is desirable to the contact angle with liquid is adjusted into 90 ° near and make capillary force ad infinitum near 0.0MN/m ²

Then, as putting down in writing in the aforementioned drying process, carry out following operation: will utilize aforementioned chemical solution to form the liquid that keeps in the recess 4 of diaphragm by drying and remove from relief pattern.At this moment, the liquid that keeps in the recess can be that diaphragm forms aforementioned cleaning fluid B or their mixed liquor that uses in the aforementioned chemical solution that uses in the operation, the back matting.Aforementioned mixed liquor forms the mode that the concentration that forms agent with the diaphragm that is contained in the chemical solution is lower than the concentration of the diaphragm formation agent in this chemical solution with diaphragm and contains; this mixed liquor can be the liquid of the state in the way of cleaning fluid B that aforementioned chemical solution is replaced into, and also can be in advance aforementioned diaphragm to be formed agent to be mixed into resulting mixed liquor among the cleaning fluid B.From the viewpoint of the purity of wafer, be preferably the mixture of water, organic solvent or water and organic solvent especially.In addition, also can temporarily with liquid behind aforementioned relief pattern surface removal, make cleaning fluid B remain in aforementioned relief pattern surface, carry out drying then.

Need to prove, under the situation of utilizing the clean (back matting) after aforementioned chemical solution carries out surface treatment, from the particle of removing aforementioned relief pattern surface, the viewpoint of impurity, the time of this operation, be to be preferably more than 10 seconds the maintained time of cleaning fluid B, more than 20 seconds more preferably.From the viewpoint of keeping effect of the water repellency of the formed diaphragm in aforementioned relief pattern surface, if with an organic solvent as cleaning fluid B, carry out the tendency that the water repellency of wafer surface is also kept in this back cleaning easily even then have.On the other hand, if the overlong time of aforementioned clean, then therefore the productivity ratio variation is preferably in 15 minutes.

In the aforementioned drying process, remove the liquid that remains in relief pattern by drying.This drying is preferably undertaken by well-known drying means such as Rotary drying method, IPA (2-propyl alcohol) steam drying, Marangoni drying (Marangoni drying), heat drying, heated-air drying, vacuumizes.

Then, as putting down in writing in the aforementioned film removal operation, remove the operation of diaphragm 10.Remove under the situation of aforementioned water repellency diaphragm, the C-C key, the C-F key that cut off in this water repellency diaphragm are effective.As its method, as long as can cut off previous key then is not particularly limited, for example, can enumerate and wafer surface is carried out illumination penetrate, wafer is heated, wafer is carried out ozone exposure, wafer surface is carried out plasma irradiating, wafer surface is carried out corona discharge etc.

Use up irradiation and remove under the situation of aforementioned diaphragm 10, preferred irradiation comprise bond energy 83kcal/mol, the 116kcal/mol of C-C key in energy and this diaphragm 10, C-F key suitable, wavelength is lower than the ultraviolet ray of 340nm, 240nm.As this light source, use metal halide lamp, low pressure mercury lamp, high-pressure mercury lamp, Excimer lamp, carbon arc etc.About ultraviolet irradiation intensity, if metal halide lamp, then for example with illuminance meter (Konica Minolta Sensing, Inc., (peak sensitivity wavelength: 365nm, mensuration wave-length coverage: measured value meter 310～400nm)) is preferably 100mW/cm for exposure intensity meter UM-10, the light receiver UM-360 of manufacturing ²More than, be preferably 200mW/cm especially ²More than.Need to prove that exposure intensity is lower than 100mW/cm ²The time, removing aforementioned diaphragm 10 can need long-time.In addition, if low pressure mercury lamp, then can the shorter ultraviolet ray of illumination wavelength, also can remove aforementioned diaphragm 10 at short notice even exposure intensity is low, thereby preferred.

In addition; use up irradiation and remove under the situation of aforementioned diaphragm 10, if in the constituent that utilizes the aforementioned diaphragm 10 of ultraviolet light degradation, produce ozone, and make the constituent voloxidation of aforementioned diaphragm 10 by this ozone; then the processing time can shorten, thereby preferred especially.As this light source, use low pressure mercury lamp, Excimer lamp etc.In addition, also can the limit carrying out illumination penetrates the limit wafer is heated.

Under the situation that wafer is heated, 400～1000 ℃, preferably 500～900 ℃ of heating of carrying out wafer.Preferably, keep this heating time 10 seconds～60 minutes, preferably kept 30 seconds～10 minutes and carry out.In addition, also can in this operation, share ozone exposure, plasma irradiating, corona discharge etc.In addition, also can heated chip limit, limit carrying out illumination penetrates.

Have by the method that adds the aforementioned diaphragm 10 of heat abstraction: the method that wafer is contacted with thermal source; Wafer is placed the method etc. of the warmed-up atmosphere of heat-treatment furnace etc.Need to prove; even wafer is placed the method for warmed-up atmosphere in the face of handling the situation of multi-disc wafer; still can easily give for the energy of removing aforementioned diaphragm 10 wafer surface; and finish processing in easy and simple to handle, short time; disposal ability is high, is industrial advantageous method.

Wafer is exposed under the situation of ozone, preferably will utilize low pressure mercury lamp etc. the ultraviolet ray irradiation, utilize high-tension low temperature discharge etc. and the ozone supply that produces in wafer surface.Also the wafer limit can be exposed in the ozone limit and carry out illumination and penetrate, also can heat.

Remove operation for aforementioned films, by with aforementioned lights irradiation, heating, ozone exposure, plasma irradiating, corona discharge combination, can remove the diaphragm of wafer surface effectively.

Embodiment

About the surface of wafer being made the cleaning fluid that keeps in face with relief pattern, the recess at least with other cleaning fluid displacement relief pattern; in other document etc., carried out various researchs; be established technology, so carry out with being evaluated as the center of chemical solution with diaphragm formation among the present invention.In addition, can find out clearly according to following formula, pattern topple over depend on largely cleaning fluid to the contact angle of wafer surface, be the contact angle of drop, and the surface tension of cleaning fluid.

P=2×γ×cosθ/S

(in the formula, γ is the surface tension of the liquid that keeps in the recess, and θ is the contact angle that the liquid that keeps in recess surface and the recess forms, and S is the width of recess.)

Recess 4 at relief pattern 2 maintains under the situation of cleaning fluid; the contact angle of drop has correlation with the capillary force (also can think aforementioned capillary force and pattern topple over be equivalence) that acts on this recess, thereby also can be according to the evaluation derivation capillary force of the contact angle of the drop of aforementioned formula and diaphragm 10.Need to prove, in an embodiment, as aforementioned cleaning fluid, used the water of the representative substances that belongs to the water system cleaning fluid.

But, have on the surface under the situation of wafer of relief pattern, can't correctly estimate the contact angle of the aforementioned diaphragm 10 self that is formed at this relief pattern surface.

About the evaluation of the contact angle of water droplet, as record among the JIS R3257 " base plate glass wettability of the surface test method " like that, drip the water droplet of number μ l on sample (base material) surface, undertaken by mensuration water droplet and the formed angle of substrate surface.Yet under the situation for wafer with pattern, it is very big that contact angle can become.This is owing to produce Wenzel effect, Cassie effect, causes contact angle to be subjected to surface configuration (roughness, influence roughness), and the cause that the contact angle of the water droplet on apparent is increased of base material.

Therefore, in the present embodiment with aforementioned chemical solution in the wafer of surface smoothing, form diaphragm in wafer surface, and this diaphragm be considered as being formed with on the surface diaphragm 10 that the surface of the wafer 1 of relief pattern 2 forms, thereby carried out various evaluations.Need to prove, in the present embodiment, as the wafer of surface smoothing, used silicon wafer at surface smoothing have titanium nitride layer " wafer of band titanium nitride film " (in table, being labeled as TiN), have " wafer of band tungsten film " (in table, being labeled as W) of tungsten layer and have " wafer of band ruthenium film " (in table, being labeled as Ru) of ruthenium layer at the silicon wafer of surface smoothing at the silicon wafer of surface smoothing.

Detailed content is as described below.Below narrated and supplied with over-protective film and form evaluation method, this diaphragm with the wafer of chemical solution and form with the preparation of chemical solution and to wafer and supply with this diaphragm formation with evaluation result behind the chemical solution.

(supplying with the evaluation method that over-protective film forms the wafer of using chemical solution)

As supplying with the evaluation method that over-protective film forms the wafer of using chemical solution, carried out the evaluation of following (1)～(4).

(1) is formed at the contact angle evaluation of the diaphragm of wafer surface

Place the about 2 μ l of pure water in the wafer surface that is formed with diaphragm, (consonance interface science company makes: the CA-X type) measure the angle (contact angle) that water droplet and wafer surface form with the contact angle meter.Herein, the contact angle of diaphragm under 50～130 ° scope, be considered as qualified.

(2) evaluation of capillary force

Use following formula to calculate P, obtain capillary force (absolute value of P).

P=2×γ×cosθ/S

Need to prove, in the present embodiment, as an example of pattern form, supposed the wafer of live width (width of recess) for the pattern of the live width of 45nm/spacing shape.Width for recess is the pattern of 45nm, is the tendency that exists pattern to be easy to topple under the situation of water at the cleaning fluid of gas-liquid interface during by relief pattern, and is the tendency that exists pattern to be difficult for toppling under the situation of 2-propyl alcohol at cleaning fluid.Be under the situation of for example titanium nitride, tungsten, ruthenium in wafer surface, the 2-propyl alcohol is 0.5 ° with respect to this surperficial contact angle, and similarly the contact angle of water is 2 °.In addition, under other the situation of the material that comprises titanium elements, W elements, ruthenium element (for example, titanium, titanium dioxide, tungsten oxide, ruthenium-oxide etc.), also be same degree.Width at recess is that 45nm, wafer surface are that cleaning fluid is that (surface tension: capillary force is 0.98MN/m to the 2-propyl alcohol in the time of 22mN/m) under the situation of titanium nitride (wafer of band titanium nitride film), tungsten (wafer of band tungsten film), ruthenium (wafer of band ruthenium film) ²On the other hand, among for the liquid beyond the removal of mercury water of surface tension maximum (surface tension: capillary force is 3.2MN/m in the time of 72mN/m) ²

(3) removal of diaphragm

Under following condition with the UV light of metal halide lamp to sample irradiation 2 hours, film is removed the removal of the diaphragm in the operation and is estimated.It is qualified that the contact angle of irradiation back water droplet is that the situation below 30 ° is considered as.

Lamp: EYE GRAPHICS Co., the M015-L312 (intensity: 1.5kW) that Ltd makes

Illumination: the measured value under the following condition is 128mW/cm ²

Determinator: (Konica Minolta Sensing, Inc. makes ultraviolet ray intensity meter, UM-10)

Light receiver: UM-360

(light-receiving wavelength: 310～400nm, spike is long: 365nm)

Mode determination: radiant illumination is measured

The surface smoothing evaluation of the wafer after (4) diaphragm is removed

(Seiko Instruments Inc. makes: SPI3700,2.5 μ m four directions scannings (square scan)) carry out surface observation, obtained the poor Δ Ra (nm) of the center line centre plane roughness Ra (nm) on the surface before and after wafer cleans by atomic force microscope.Need to prove that Ra calculates by following formula in the mode of " average absolute of the difference from the datum level to the given side " for the center line average roughness with JIS B0601 definition is applicable to mensuration face and the value that obtains to three-dimensional extended.

Ra = \frac{1}{S_{0}} {&Integral;}_{Y_{T}}^{Y_{B}} {&Integral;}_{X_{L}}^{X_{R}} | F (X, Y) - Z_{0} | dXdY

Herein, X _L, X _R, Y _B, Y _TRepresent Building X mark, Building Y target measurement range respectively.S ₀Being the area of mensuration face when being the ideal plane, is (X _R-X _L) * (Y _B-Y _T) value.In addition, F (X, Y) expression measuring point (X, height Y), Z ₀Average height in the expression mensuration face.

Measure the Ra value of the wafer surface before diaphragm forms and the Ra value of having removed the wafer surface behind the diaphragm; if both poor (Δ Ra) be ± 1nm in; then be considered as not having the residue of aforementioned diaphragm because cleaning makes wafer surface generation etch and wafer surface, it is qualified to be considered as.

[embodiment 1]

(I-1) diaphragm forms the preparation with chemical solution

Mixing forms the octadecyl phosphonic acids (C of agent as the water repellency diaphragm ₁₈H ₃₇P (O) (OH) ₂) 0.002g, as the propylene glycol monomethyl ether of solvent (below be designated as " PGMEA ") 99.998g; stirred 18 hours, obtaining forming the concentration (below be designated as " diaphragm formation agent concentration ") that forms agent with the aforementioned diaphragm of the total amount of chemical solution with respect to diaphragm is the diaphragm formation chemical solution of 20 quality ppm.

(I-2) matting of wafer (pretreatment procedure)

As pretreatment procedure 2, the wafer (surface has the silicon wafer of the titanium nitride layer of thickness 50nm) of level and smooth band titanium nitride film is immersed in the aqueous hydrogen peroxide solution of 1 quality % 1 minute in room temperature, then be immersed in the pure water 1 minute, and then as pretreatment procedure 3, dipping is 1 minute in isopropyl alcohol (below be designated as " iPA ").

(I-3) diaphragm of wafer surface forms operation～drying process

Form operation as diaphragm, under 20 ℃, will form with flooding 10 minutes in the chemical solution with wafer prepared diaphragm in above-mentioned " (I-1) diaphragm forms the preparation with chemical solution " of titanium nitride film, form diaphragm in this wafer surface thus.Thereafter, as the back matting, be with the wafer of titanium nitride film to flood in iPA 1 minute this, as drying process, will be with the wafer of titanium nitride film to take out from iPA, injection air is removed the iPA on surface.

Main points according to record in above-mentioned " the supply over-protective film forms the evaluation method with the wafer of chemical solution " are estimated the wafer of resulting band titanium nitride film; the result is as shown in table 1; initial contact angle before the surface treatment is lower than 10 °; and the contact angle after the surface treatment is 106 °, has shown that excellent water repellency gives effect.In addition, use the formula of record in above-mentioned " evaluation of capillary force " to calculate capillary force when maintaining water, capillary force is 0.9MN/m as a result ², capillary force is little.In addition, the postradiation contact angle of UV is lower than 10 °, and diaphragm is removed.Can confirm that in addition the Δ Ra value of the postradiation wafer of UV is in ± 0.5nm, wafer and then does not have the residue of residual diaphragm not by etch during cleaning after the UV irradiation.

[table 1]

[embodiment 2～84]

Solvent, diaphragm that the diaphragm formation agent of use among the suitable change embodiment 1, diaphragm form with chemical solution form the time of agent concentration, diaphragm formation operation, the temperature of diaphragm formation operation, the cleaning fluid of back matting; carry out the surface treatment of wafer, and then carry out its evaluation.Show the result in table 1～table 3.

[table 2]

[table 3]

Need to prove, in table, " C ₁₂H ₂₅P (O) (OH) ₂" refer to dodecyl phosphonic acids, " C ₁₀H ₂₁P (O) (OH) ₂" refer to decylphosphonic acid, " C ₁₀H ₂₁P (O) (OC ₂H ₅) ₂" refer to decylphosphonic acid diethylester, " C ₈H ₁₇P (O) (OH) ₂" refer to octyl phosphonic acid, " C ₆F ₁₃-C ₂H ₄-P (O) (OH) ₂" refer to perfluoro hexyl ethylphosphonic acid, " C ₄F ₉-C ₂H ₄-P (O) (OH) ₂" refer to perfluoro butyl ethylphosphonic acid, " C ₆H ₁₃P (O) (OH) ₂" refer to hexyl phosphonic acids, " C ₄H ₉P (O) (OH) ₂" refer to butyl phosphonic acids, " C ₆H ₅P (O) (OH) ₂" refer to phenyl-phosphonic acid.In addition, " PGME " refers to propylene glycol monomethyl ether, " DEGME " refers to diethylene glycol monomethyl ether, " DEGDEE " refers to diethylene glycol diethyl ether, " DEGEEA " refers to the TC acetic acid esters, " GBL " refers to gamma-butyrolacton, " PGDA " refers to propylene-glycol diacetate, and " TPGDME " refers to the tripropylene glycol dimethyl ether, and " 13BGDA " refers to 1,3-butanediol diacetate esters, " 14BGDA " refers to 1,4-butanediol diacetate esters, and " DPGMEA " refers to the dipropylene glycol monomethyl ether acetate, " TEGBME " refers to triethylene glycol butyl methyl ether, and " TEGDME " refers to the triethylene glycol dimethyl ether.In addition, " PGMEA/iPA " refers to solvent that PGMEA and iPA are mixed with mass ratio 99.5:0.5, in addition, " DEGEEA/iPA " refers to solvent that DEGEEA and iPA are mixed with mass ratio 99.5:0.5, " DEGEEA/iPA/ water " refers to solvent that DEGEEA and iPA and water are mixed with mass ratio 94.9:0.1:5, " GBL/iPA " refers to solvent that GBL and iPA are mixed with mass ratio 95:5, " GBL/iPA/ water " refers to solvent that GBL and iPA and water are mixed with mass ratio 95:4:1, " PGDA/iPA " refers to solvent that PGDA and iPA are mixed with mass ratio 99.5:0.5, " PGDA/iPA/ water " refers to solvent that PGDA and iPA and water are mixed with mass ratio 94.9:0.1:5, " TPGDME/iPA " refers to solvent that TPGDME and iPA are mixed with mass ratio 99.5:0.5, " 13BGDA/iPA " refers to solvent that 13BGDA and iPA are mixed with mass ratio 99.5:0.5, " 13BGDA/iPA/ water " refers to solvent that 13BGDA and iPA and water are mixed with mass ratio 94.9:0.1:5, " 14BGDA/iPA " refers to solvent that 14BGDA and iPA are mixed with mass ratio 99.5:0.5, " DPGMEA/iPA " refers to solvent that DPGMEA and iPA are mixed with mass ratio 99.5:0.5, " DPGMEA/iPA/ water " refers to solvent that DPGMEA and iPA and water are mixed with mass ratio 94.9:0.1:5, " TEGBME/iPA " refers to solvent that TEGBME and iPA are mixed with mass ratio 99.5:0.5, " TEGBME/iPA/ water " refers to solvent that TEGBME and iPA and water are mixed with mass ratio 94.9:0.1:5, " GBL/DPGMEA/iPA " refers to solvent that GBL and DPGMEA and iPA are mixed with mass ratio 49.75:49.75:0.5, " GBL/DPGMEA/iPA/ water " refers to solvent that GBL and DPGMEA and iPA and water are mixed with mass ratio 47.45:47.45:0.1:5, " GBL/PGMEA/iPA " refers to solvent that GBL and PGMEA and iPA are mixed with mass ratio 49.75:49.75:0.5, " GBL/PGMEA/iPA/ water " refers to solvent that GBL and PGMEA and iPA and water are mixed with mass ratio 47.45:47.45:0.1:5, " DEGEEA/PGME-3 " refers to solvent that DEGEEA and PGME are mixed with mass ratio 97:3, " DEGEEA/iPA-2 " refers to solvent that DEGEEA and iPA are mixed with mass ratio 98:2, " TEGBME/iPA-2 " refers to solvent that TEGBME and iPA are mixed with mass ratio 98:2, " GBL/DPGA/iPA/ water " refers to solvent that GBL and DPGA and iPA and water are mixed with mass ratio 47.45:47.45:0.1:5, " GBL/13BGDA/iPA/ water " refers to solvent that GBL and 13BGDA and iPA and water are mixed with mass ratio 47.45:47.45:0.1:5, " GBL/TEGBME/iPA/ water " refers to solvent that GBL and TEGBME and iPA and water are mixed with mass ratio 47.45:47.45:0.1:5, " GBL/DEGEEA/iPA/ water " refers to that solvent that GBL and DEGEEA and iPA and water are mixed with mass ratio 47.45:47.45:0.1:5, " DEGEEA/PGME-10 " refer to the solvent that DEGEEA and PGME are mixed with mass ratio 90:10.

[embodiment 85]

(II-1) diaphragm forms the preparation with chemical solution

Mixing forms the octadecyl phosphonic acids (C of agent as the water repellency diaphragm ₁₈H ₃₇P (O) (OH) ₂) 0.002g, as the PGMEA99.998g of organic solvent, stirred 18 hours, it is that the diaphragm of 20 quality ppm forms and uses chemical solution that the film that is protected forms agent concentration.

(II-2) matting of wafer (pretreatment procedure)

As pretreatment procedure 2, the wafer (surface has the silicon wafer of the tungsten layer of thickness 50nm) of level and smooth band tungsten film is immersed in the ammoniacal liquor of 1 quality % 1 minute in room temperature, then be immersed in the pure water 1 minute, and then as pretreatment procedure 3, dipping is 1 minute in iPA.

(II-3) diaphragm of wafer surface forms operation～drying process

Form operation as diaphragm, under 20 ℃, will form with flooding 10 minutes in the chemical solution with wafer prepared diaphragm in above-mentioned " (II-1) diaphragm forms the preparation with chemical solution " of tungsten film.As back matting, be with the wafer of tungsten film among iPAs flood 1 minute this thereafter.As drying process, will be with the wafer of tungsten film to take out from iPA, injection air is removed the iPA on surface.

Main points according to record in above-mentioned " the supply over-protective film forms the evaluation method with the wafer of chemical solution " are estimated the wafer of resulting band tungsten film; the result is as shown in table 4; initial contact angle before the surface treatment is lower than 10 °; and the contact angle after the surface treatment is 68 °, has shown that water repellency gives effect.In addition, use the formula of record in above-mentioned " evaluation of capillary force " to calculate capillary force when maintaining water, capillary force is 1.2MN/m as a result ², capillary force is little.In addition, the postradiation contact angle of UV is lower than 10 °, and diaphragm can be removed.Can confirm that in addition the Δ Ra value of the postradiation wafer of UV is in ± 0.5nm, wafer and then does not have the residue of residual diaphragm not by etch during cleaning after the UV irradiation.

[table 4]

[embodiment 86～109]

The diaphragm formation agent of using among the suitable change embodiment 85, solvent, diaphragm formation agent concentration, diaphragm form the temperature of operation, carry out the surface treatment of wafer, and then carry out its evaluation.Show the result in table 4.

[embodiment 110]

(III-1) diaphragm forms the preparation with chemical solution

(III-2) matting of wafer (pretreatment procedure)

As pretreatment procedure 2, the wafer (surface has the silicon wafer of the ruthenium layer of thickness 300nm) of level and smooth band ruthenium film is immersed in the ammoniacal liquor of 1 quality % 1 minute in room temperature, then be immersed in the pure water 1 minute, and then as pretreatment procedure 3, dipping is 1 minute in iPA.

(III-3) diaphragm of wafer surface forms operation～drying process

Form operation as diaphragm, under 20 ℃, will form with flooding 10 minutes in the chemical solution with wafer prepared diaphragm in above-mentioned " (III-1) diaphragm forms the preparation with chemical solution " of ruthenium film.As back matting, be with the wafer of ruthenium film among iPAs flood 1 minute this thereafter.As drying process, will be with the wafer of ruthenium film to take out from iPA, injection air is removed the iPA on surface.

Main points according to record in above-mentioned " the supply over-protective film forms the evaluation method with the wafer of chemical solution " are estimated the wafer of resulting band ruthenium film; the result is as shown in table 5; initial contact angle before the surface treatment is lower than 10 °; and the contact angle after the surface treatment is 72 °, has shown that water repellency gives effect.In addition, use the formula of record in above-mentioned " evaluation of capillary force " to calculate capillary force when maintaining water, capillary force is 1.0MN/m as a result ², capillary force is little.In addition, the postradiation contact angle of UV is lower than 10 °, and diaphragm can be removed.Can confirm that in addition the Δ Ra value of the postradiation wafer of UV is in ± 0.5nm, wafer and then does not have the residue of residual diaphragm not by etch during cleaning after the UV irradiation.

[table 5]

[embodiment 111～136]

The diaphragm formation agent of using among the suitable change embodiment 110, solvent, diaphragm formation agent concentration, diaphragm form the temperature of operation, carry out the surface treatment of wafer, and then carry out its evaluation.Show the result in table 5.

[comparative example 1]

Except diaphragm formation is not supplied to the wafer of band titanium nitride film with chemical solution, identical with embodiment 1.That is, in this comparative example, the wafer surface that does not form diaphragm is estimated.Evaluation result is as shown in table 6, and the contact angle of wafer is low to moderate 14 °, and the capillary force when maintaining water is greatly to 3.1MN/m ²

[table 6]

[comparative example 2]

At first, mix silane coupler the trimethylsilyl chloride ((CH that forms agent as diaphragm ₃) ₃SiCl) it is that the diaphragm of 30000 quality ppm forms and uses chemical solution that 3g and as the toluene 97g of solvent, stir about 5 minutes, the film that is protected form agent concentration.Then, utilization method similarly to Example 1 is with cleaning and the surface treatment of the wafer of titanium nitride film.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 18 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.0MN/m ², capillary force is big.

[comparative example 3]

Except using hexamethyldisiloxane ([(CH ₃) ₃Si] ₂NH) as beyond the diaphragm formation agent, identical with comparative example 2.The result is as shown in table 6, and the contact angle after the surface treatment is 20 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.0MN/m ², capillary force is big.

[comparative example 4]

Except using trimethyl silyl dimethyl amine ((CH ₃) ₃SiN (CH ₃) ₂) as beyond the diaphragm formation agent, identical with comparative example 2.The result is as shown in table 6, and the contact angle after the surface treatment is 20 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.0MN/m ², capillary force is big.

[comparative example 5]

Except diaphragm formation is not supplied to the wafer of band tungsten film with chemical solution, identical with embodiment 85.That is, in this comparative example, the wafer surface that does not form diaphragm is estimated.Evaluation result is as shown in table 6, and the contact angle of wafer is low to moderate 14 °, and the capillary force when maintaining water is greatly to 3.1MN/m ²

[comparative example 6]

At first, mix silane coupler the trimethylsilyl chloride ((CH that forms agent as diaphragm ₃) ₃SiCl) it is that the diaphragm of 30000 quality ppm forms and uses chemical solution that 3g and as the toluene 97g of solvent, stir about 5 minutes, the film that is protected form agent concentration.Then, utilize and cleaning and the surface treatment of the same method of embodiment 85 with the wafer of tungsten film.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 14 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.1MN/m ², capillary force is big.

[comparative example 7]

Except using hexamethyldisiloxane ([(CH ₃) ₃Si] ₂NH) as beyond the diaphragm formation agent, identical with comparative example 6.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 8 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.2MN/m ², capillary force is big.

[comparative example 8]

Except using trimethyl silyl dimethyl amine ((CH ₃) ₃SiN (CH ₃) ₂) as beyond the diaphragm formation agent, identical with comparative example 6.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 10 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.2MN/m ², capillary force is big.

[comparative example 9]

Except diaphragm formation is not supplied to the wafer of band ruthenium film with chemical solution, identical with embodiment 110.That is, in this comparative example, the wafer surface that does not form diaphragm is estimated.Evaluation result is as shown in table 6, and the contact angle of wafer is low to moderate 14 °, and the capillary force when maintaining water is greatly to 3.1MN/m ²

[comparative example 10]

At first, mix silane coupler the trimethylsilyl chloride ((CH that forms agent as diaphragm ₃) ₃SiCl) it is that the diaphragm of 30000 quality ppm forms and uses chemical solution that 3g and as the toluene 97g of solvent, stir about 5 minutes, the film that is protected form agent concentration.Then, utilize and cleaning and the surface treatment of the same method of embodiment 110 with the wafer of ruthenium film.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 14 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.1MN/m ², capillary force is big.

[comparative example 11]

Except using hexamethyldisiloxane ([(CH ₃) ₃Si] ₂NH) as beyond the diaphragm formation agent, identical with comparative example 10.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 20 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.0MN/m ², capillary force is big.

[comparative example 12]

Except using trimethyl silyl dimethyl amine ((CH ₃) ₃SiN (CH ₃) ₂) as beyond the diaphragm formation agent, identical with comparative example 10.Evaluation result is as shown in table 6, and the contact angle after the surface treatment is 22 °, does not observe water repellency and gives effect.Capillary force when in addition, maintaining water is 3.0MN/m ², capillary force is big.

Description of reference numerals

1 wafer

The relief pattern of 2 wafer surface

The protuberance of 3 patterns

The recess of 4 patterns

The width of 5 recesses

The height of 6 protuberances

The width of 7 protuberances

8 diaphragms that remain in recess 4 form uses chemical solution

9 remain in the liquid of recess 4

10 diaphragms

Claims

1. a water repellency diaphragm forms and uses chemical solution; it is characterized in that; it is to comprise the chemical solution that following water repellency diaphragm forms agent and solvent; described water repellency diaphragm forms agent and has titanium for the recess surface that is formed with relief pattern and this relief pattern on the surface; tungsten; aluminium; copper; tin; form the water repellency diaphragm in recess surface at least after the matting of the wafer of at least a kind of element in tantalum and the ruthenium and before the drying process; this water repellency diaphragm forms the compound that agent is following general formula [1] expression

In the formula [1], R ¹Be that the optional carbon number that is replaced by fluorine element of part or all protium is 1 to 18 1 valency alkyl, R ²Be to comprise the 1 valency organic group that the optional carbon number that is replaced by fluorine element of part or all protium is 1 to 18 alkyl separately independently of each other, a is 0 to 2 integer.

2. water repellency diaphragm according to claim 1 forms and uses chemical solution, it is characterized in that, described water repellency diaphragm forms the compound that agent is following general formula [2] expression,

In the formula [2], R ³Be that the optional carbon number that is replaced by fluorine element of part or all protium is 1 to 18 1 valency alkyl.

3. water repellency diaphragm; it is characterized in that; it has for the recess surface that is formed with relief pattern and this relief pattern on the surface after the matting of wafer of a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium and before the drying process at least; claim 1 or the described water repellency diaphragm formation of claim 2 are remained in this recess at least with chemical solution; thereby at the water repellency diaphragm of recess surface formation, this water repellency diaphragm is to be formed by the compound that the described general formula [1] that forms agent as the water repellency diaphragm is represented at least.

4. a cleaning method is characterized in that, it is the cleaning method that the surperficial recess surface that is formed with relief pattern and this relief pattern has the wafer of at least a kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and the ruthenium, and this method has following operation at least:

The drying process of liquid being removed from relief pattern by drying;

Remove the film of diaphragm and remove operation,

It is to comprise the chemical solution that forms agent for the water repellency diaphragm that forms the water repellency diaphragm in described at least recess surface that described diaphragm forms with chemical solution,

Described water repellency diaphragm is to be formed by the compound that the described general formula [1] that forms agent as the water repellency diaphragm is represented.